JP2014504583A - Base material with a stack with thermal properties, especially for producing heated glass - Google Patents

Abstract

  The present invention relates to n (n is an integer of 3 or more) metal functional layers, in particular, metal functional layers (40, 80, 120) based on silver or a metal alloy containing silver, and at least one non-reflective layer Alternately n + 1 non-reflective coatings (20, 60, 100, 140), and each of the functional layers (40, 80, 120) has two non-reflective coatings (20, 60, 100, 140). ), A substrate (10) with a stack of thin layers, in particular a transparent glass substrate, each functional layer (40, 80, 120) being two non-reflective coatings (20, 60) , 100, 140), each substrate being a substrate (10) comprising at least one non-reflective layer, wherein the stack is the first as viewed from the substrate. Non-layer under the functional layer (40) Each of the reflective coating (20) and the non-reflective coating on the last functional layer as viewed from the substrate includes at least one high refractive index non-reflective layer and between the two functional layers. At least two high-refractive index non-reflective layers (25, 145) each having a refractive index of 2.15 or more so that each non-reflective coating (60, 100) disposed in It is related with the base material (10) characterized by including this.

Description

  The present invention is a transparent substrate made of a rigid inorganic material such as glass in particular, and is a thin film multilayer body having a plurality of functional films capable of acting on solar radiation and / or long wavelength infrared radiation. It relates to a coated transparent substrate.

  More specifically, the present invention relates to a base material, particularly a transparent glass base material, and “n” metal functional film, in particular, a metal functional film composed on the basis of silver or a metal alloy containing silver. And (n + 1) antireflection coatings alternately so that each functional film is disposed between two antireflection coatings, and n is an integer of 3 or more. It is related with the base material provided with. Each antireflection coating comprises at least one antireflection film, and each antireflection coating is preferably composed of at least one film or a plurality of films, and the one film or each film is an antireflection film. is there.

  The present invention more specifically relates to the production of thermal insulation and / or solar protection glazing units using such substrates. These glazing units, in particular, reduce the load associated with air conditioning and / or prevent overheating (referred to as “solar control” glass) and / or use of the surface on which the building surface and the vehicle cabin glass are arranged. It is intended to be installed on both buildings and vehicles for the purpose of reducing the amount of energy dissipated outside (called “low-E” or “low-emission” glass) resulting from the increase. Also good.

  These substrates may in particular be integrated into electronics, and the multilayer body can thereby act as an electrode for carrying current (lighting devices, display devices, photovoltaic panels, electrochromic Or a glazing unit having a specific purpose, such as a heated glazing unit, in particular a heated windshield for a vehicle.

  In the context of the present invention, reference to a multilayer body comprising a plurality of functional films shall be understood to mean a multilayer body comprising at least three functional films.

  A multilayer body composed of a plurality of functional films is known.

  In this type of multilayer body, each functional film is placed between two anti-reflective coatings, each of these anti-reflective coatings generally being nitrides, in particular silicon nitride or aluminum nitride, and / or oxidation. A plurality of antireflection films each formed from an object are provided. From an optical point of view, the purpose of placing these anti-reflection coatings on both sides of the functional film is to make the functional film “anti-reflective”. In some cases, these antireflection films are called “dielectric films” in contrast to the metallic (and therefore conductive) properties of the functional film.

  However, in some cases, a very thin blocker coating may be inserted between each of the anti-reflective coating or anti-reflective coatings and the adjacent functional film. This blocker coating is placed below the functional film in the substrate direction and / or on the functional film opposite to the substrate, during the subsequent application of the anti-reflection coating, This functional film is protected from degradation that tends to occur during any high temperature heat treatment, such as enhanced heat treatment.

  These blocker coatings are not part of the anti-reflective coating. This is because blocker coatings are generally not considered when defining the optical properties of the multilayer body.

  A multilayer body composed of a plurality of functional films is known from the prior art, for example, the prior art of WO 2005/051858.

  The antireflective film used in the multilayer body with three or four functional films presented in the above document is what is called a “medium” refractive index film, that is, a film having a refractive index that is neither high nor low. It is customary to be considered.

  Specifically, in a thin film multilayer, a “low” refractive index film has a refractive index of 1.60 or less, and a “medium” refractive index film has a refractive index in the range of greater than 1.60 and less than 2.15. The “high” refractive index film typically has a refractive index of 2.15 or higher.

  It will be recalled that n represents the actual refractive index of the material at a given wavelength and k represents the imaginary part of the refractive index at the given wavelength.

  In this specification, the refractive index of the film is a refractive index measured at a wavelength of 550 nm, and as a rule, the refractive index is given to the second decimal place without rounding off for simplification. The extinction coefficient k is also given at a wavelength of 550 nm.

  The exemplary configuration described in WO 2005/051858 does not appear to be completely satisfactory.

  In many applications, it is desirable to keep the sheet resistance of the multilayer body low, while keeping the light transmittance of the multilayer body (and thus the light transmittance of the glazing unit incorporating the multilayer body) high and / or While the sheet resistance of the multilayer body is kept low, it is desirable that the light reflectance of the multilayer body (and thus the light reflectance of the glazing unit incorporating the multilayer body) is lower and / or the sheet resistance of the multilayer body is low. It is desirable that the reflected color is less noticeable while being maintained, and the value measured by, for example, the Lab system is close to zero. The low sheet resistance here means a resistance of 1 Ω / □ or less.

Prior art includes European Patent Application No. 2030954.
In this document, at least two films are referred to as “dielectric absorber” films, which are further “neutral” absorbers, one of which “dielectric absorber” films comprises at least two metal functional films. The multilayer body is disposed below the first metal functional film as viewed from the base material, and the other “dielectric absorber” film is disposed on the last metal functional film of the multilayer body as viewed from the base material. Has been placed.

  The dielectric absorption film of the above document has a non-negligible extinction coefficient k of at least 0.1.

  For this reason, the dielectric absorption film of the above-mentioned document is evaluated as “dielectric” in order to distinguish it from a metal functional film exhibiting a certain degree of absorption. For reference, the absorbance k of silver used for the production of the functional metal film is about 3.34 at a wavelength of 550 nm.

  Furthermore, the “neutral” absorption actually corresponds to a balanced absorption in the visible wavelength region, with a short wavelength (380 <λ <450 nm) relative to the extinction coefficient k at a long wavelength in the visible region (650 <λ <760 nm). The ratio of the extinction coefficient k is balanced, i.e. about 1, and more precisely between 0.52 and 1.9.

  The aim of the solution of the above document is to increase the ability of the multilayer body to absorb solar radiation (especially infrared), and by using a neutral absorbing film and arranging the film in a specific manner in the multilayer body, It is to provide a color that is evaluated as “comfortable” in the above-mentioned document.

  The inevitable consequence of this solution is that the multilayer body absorbs not only in the infrared wavelength region but also in the visible wavelength region in a non-negligible manner, so that the multilayer body has a high light transmittance in the visible region. It is a point that you cannot have.

International Publication No. 2005/051858 Pamphlet European Patent Application No. 2030954

  7 and 8 of European Patent Application No. 2030954 show the extinction coefficient k and refractive index n of two silicon nitride compounds and titanium nitride compounds, respectively, one of which is titanium nitride (TiN) 45. % And 55% silicon nitride, the other contains 71% titanium nitride (TiN) and 29% silicon nitride.

The absorbance k of TiN at 550 nm is about 1.88, and the absorbance k of Si ₃ N _{4 at} 550 nm is about 0.0135. Logically, FIG. 7 shows that the k values of the two compounds are between these two numbers. Furthermore, FIG. 7 shows that the k values of the two compounds are relatively high, so adding Si ₃ N ₄ by 29% and 55% to TiN has little effect on TiN absorbance k. It shows that there is no.

The refractive index of TiN at 550 nm is about 0.97, and the refractive index of Si ₃ N _{4 at} 550 nm is about 2.02. Theoretically, the refractive index of a compound consisting of a mixture of these two materials is expected to fall between these two values. However, quite unexpectedly, FIG. 8 shows that the refractive index of the compound at 550 nm is higher than that of Si ₃ N ₄ , ie between 2.4 and 2.5. This is therefore inconsistent. Furthermore, with regard to the weak “dilution” of TiN extinction coefficient k shown in FIG. 7 with Si ₃ N ₄ , FIG. 8 is predicted to show that the refractive index of the two compounds is low, and Si ₃ N ₄ is added. However, FIG. 8 is increasingly inconsistent.

In fact, a compound made of a mixture of silicon nitride and titanium nitride necessarily has a refractive index that falls between the refractive index of Si ₃ N _{4 and} the refractive index of TiN.

  The object of the present invention is to provide a multilayer body having a very low sheet resistance, in particular that a glazing unit incorporating this multilayer body can exhibit high energy reflectivity and / or very low emissivity, and And / or has a very low sheet resistance, especially when laminated, so that it can be heated by passing current between two bus bars electrically connected to the multilayer body It is to provide a multilayer body having a high light transmission and a relatively intermediate color, these properties preferably being one (or more) high temperature bending and / or strengthening And / or after slow cooling heat treatment, or these properties are obtained before one or more high temperature bending and / or strengthening and / or slow cooling heat treatment, and these properties may be (Or Is maintained within a limited range regardless of whether the subject of the above) the heat treatment. Needless to say, the light transmittance and the light reflectance referred to in the present specification are the light transmittance and the light reflectance in the visible wavelength region.

  Accordingly, one of the objects of the present invention is, in its broadest sense, the substrate according to claim 1, particularly a transparent glass substrate. The dependent claims define advantageous embodiments of the substrate.

  As described above, the substrate according to the present invention includes “n” metal functional films, in particular, a functional film based on silver or a metal alloy containing silver, and at least one antireflection film, “(n + 1). ) "Antireflection coatings, each comprising a thin film multilayer body in which each functional film is disposed between two antireflection coatings, where n is an integer of 3 or more is there. The present invention is particularly suitable for a multilayer body including n = 3 or n = 4 functional films.

  The substrate includes at least one antireflection coating disposed below the first functional film as viewed from the substrate and at least one antireflection coating disposed on the last functional film as viewed from the substrate. Each antireflective coating that includes a high refractive index antireflective film and that is disposed between two functional films does not include a high refractive index antireflective film (ie, each reflective disposed between two functional films The multilayer coating comprises at least two high refractive antireflective coatings each having a refractive index of 2.15 or greater, such that the anti-reflection coating does not include a high refractive index antireflective coating having a refractive index of 2.15 or greater. It should be noted in that it includes.

  Due to its essential characteristics, in the technical field to which the present invention pertains, the term “antireflection” customarily refers to a non-absorbing film, so the antireflection film cannot be an absorbing film.

  The high refractive index film according to the present invention can be regarded as a transparent film in this respect. This is because they are non-absorptive and have an extinction coefficient k below 0.1 which is not negligible or even below 0.01.

  For even more prominent reasons, the high refractive index film according to the present invention does not exhibit “neutral” absorption, but has a balanced absorption in the visible wavelength range, ie absorption at long wavelengths (650 <λ <760 nm) in the visible wavelength range. The ratio of the absorptance k at the short wavelength (380 <λ <450 nm) in the same visible wavelength range to the rate k is balanced, ie about 1, more precisely between 0.52 and 1.9. Does not show a balanced absorption that is contained in This is because it is only this ratio that is meaningful for non-negligible k values.

  These high-refractive-index films according to the present invention can also be called “high-refractive-index dielectric antireflection films” in the sense of contrasting with the metallic (and therefore conductive) properties of the functional film.

  The antireflective coating disposed below the first functional film as viewed from the substrate is preferably one or more high refractive index antireflective films, followed by 1.60, as viewed from the substrate. A medium refractive index wet antireflective coating having a refractive index excluding these values, optionally doped with at least one other element such as aluminum And a wet antireflective coating based on zinc oxide.

  In a particular variant, the antireflective coating disposed on the last functional film as viewed from the substrate consists only of one or more high refractive index antireflective films, so that it is a medium refractive index film or a low refractive index film. Not included.

Preferably, at least one or each high refractive index anti-reflective coating is based on zirconium silicon nitride. Other possible materials for the high refractive index anti-reflective coating are MnO (refractive index 2.16 at wavelength 550 nm), WO ₃ (refractive index 2.15 at wavelength 550 nm), Nb ₂ O ₅ (refractive at wavelength 550 nm). 2.3), Bi ₂ O ₃ (refractive index 2.6 at a wavelength of 550 nm) and Zr ₃ N ₄ (refractive index 2.55 at a wavelength of 550 nm).

  Thin high refractive index films are known to have a refractive index of up to 3.1 at 550 nm. Each of the high refractive index antireflection films according to the present invention preferably has a refractive index of 2.6 or less, and more preferably 2.3 or less.

  If a high refractive index film based on zirconium silicon nitride is selected, the ratio of silicon to zirconium is preferably 40% Si to 25% to 45% Zr to obtain the desired high refractive index. Of course, the total amount of the target product is 100% by weight.

When the ratio of silicon is high (over 40% by weight in the target product), it is conceivable to increase the conductivity of the target product using another element such as Al. In this case, in order to obtain a desired refractive index, it is preferable that the elements Si, Zr, and Al are present in the target product in the following ranges by weight ratio, and of course, the target product has a total of 100% by weight. is there.
Si: 45% to 75% (including these values)
Zr: 20% to 50% (including these values)
-Al: 1% to 10% (including these values)

  Furthermore, when the one or more high refractive index films of the last antireflective coating are one or more nitride films, the antireflective coating disposed on the last functional film as viewed from the substrate is a multilayer body. In order to make the manufacturing easier, it is preferable to consist only of a nitride film.

Furthermore, it is preferred that the at least one or each high refractive index antireflection film is not based on titanium oxide TiO ₂ or TiO _y .

In the modified example, the thickness e _x of each functional film of the multilayer body (that is, the functional film in at least the second row and the third row when viewed from the base material) is the thickness of the functional film located in front of the base material. It is smaller than the thickness, and it is e _x = αe _x-1 (where x is a number indicating the number of functional films in the row when viewed from the base material, and x-1 is a function located in front of the base material) A number indicating the column number of the membrane, α is a number such that 0.5 ≦ α <1, preferably 0.55 ≦ α ≦ 0.95, or 0.6 ≦ α ≦ 0.95) It is like that.

In another variation, the thickness e _x of each functional film of the multilayer body (that is, the functional film in at least the second row and the third row as viewed from the base material) is the functional film positioned forward in the base material direction. be the same as the thickness of, and it in e _x = αe _x-1 (wherein, x is a number indicating what row of the functional film when viewed from the substrate, x-1 before the substrate direction Is a number indicating the column number of the functional film located at, and α is 0.85 ≦ α <1.15, preferably 0.90 ≦ α ≦ 1.1, or 0.95 ≦ α ≦ 1.05 Is such a number).

  The term “row” in the present invention is understood to mean an integer number of each functional film as viewed from the substrate. That is, the functional film closest to the base material is the functional film in the first row, the functional film next to the base material is the functional film in the second row, and the like.

The thickness of the first metal functional film (that is, that of the first row) when viewed from the substrate is, for example, 10 nm ≦ e ₁ ≦ 18 nm, preferably 11 nm ≦ e ₁ ≦ 15 nm.

Therefore, in the case of 0.55 ≦ α ≦ 0.95, the thickness of the first metal functional film from the substrate is such that 10 nm ≦ e ₁ ≦ 18 nm, preferably 11 nm ≦ e ₁ ≦ 15 nm, In the case of 0.6 ≦ α ≦ 0.95, the thickness of the first metal functional film from the substrate is such that 10 nm ≦ e ₁ ≦ 18 nm, preferably 11 nm ≦ e ₁ ≦ 15 nm.

Further, if 0.6 ≦ α ≦ 0.9, the thickness of the first metal functional film as viewed from the substrate is 10 nm ≦ e ₁ ≦ 18 nm, preferably 11 nm ≦ e ₁ ≦ 15 nm. Or 0.6 ≦ α ≦ 0.85, the thickness of the first metal functional film as viewed from the substrate is 10 nm ≦ e ₁ ≦ 18 nm, preferably 11 nm ≦ e ₁ ≦ 15 nm. It can be

Furthermore, since the essential object of the present invention is to provide a multilayer body having a low sheet resistance, the total thickness of the metal functional film is preferably more than 30 nm, particularly when 11 nm ≦ e ₁ ≦ 15 nm. Large, in particular between 30 and 60 nm (inclusive of these values), or this total thickness is between 35 and 50 nm in the case of a thin film multilayer with three functional films, or this total thickness This is between 40 nm and 60 nm in the case of a thin film multilayer having four functional films.

Preferably, the value of α is different for all functional films in the second and subsequent columns of the multilayer body to which the formula e _x = αe _x-1 is applied (at least 0.02 or at least 0.05).

  It should be noted here that the decrease in the thickness distribution is not the decrease in the distribution of all the films of the multilayer body (considering the antireflection film), but only the decrease in the thickness distribution of the functional film. is important.

  In a multilayer body having a functional film of decreasing thickness as viewed from the substrate, the functional films all have different thicknesses. However, in this case, the distribution of the thickness of the functional film in the multilayer body is different from that obtained by the structure having the functional film having a certain thickness or the structure having the functional film having an increased thickness as viewed from the substrate. A much better sheet resistance can be obtained unexpectedly.

  Unless otherwise noted, the thicknesses given herein are physical or actual thicknesses (not optical thicknesses).

  Furthermore, when the vertical position of the membrane (eg below / up) is mentioned, the supporting substrate is always considered to be horizontally and bottom with the multilayer body above it. It is. When it is specified that a film is deposited directly on another film, it means that there is no (or more) intermediate film between these two films. Here, the rows of functional films are always defined in view of the substrate that supports the multilayer body (the substrate on which the multilayer body is deposited on the surface).

  The thickness of each functional film is preferably in the range between 8 nm and 20 nm (including these values), or in the range between 10 nm and 18 nm (including these values), more preferably between 11 nm and 15 nm. (Including these values).

  The total thickness of the functional metal film is preferably greater than 30 nm, in particular in the range between 30 nm and 60 nm (inclusive of these values), or the total thickness of the thin film multilayer having three functional films. The case is between 35 nm and 50 nm, or the total thickness is between 40 nm and 60 nm in the case of a thin film multilayer having four functional films.

  The multilayer body according to the present invention is a low sheet whose sheet resistance R is preferably 1 Ω / □ or less after an optional heat treatment of bending, strengthening or slow cooling type, or alternatively 1 Ω / □ or less before the heat treatment. Resistive multilayers because such treatment generally reduces sheet resistance.

  In a particular variant, each antireflective coating that is arranged between two functional films and does not have a high refractive index antireflective film comprises at least one antireflective film based on silicon nitride, Optionally doped with at least one other element such as aluminum.

  In a particular variant of the invention, the last film of each antireflection coating underneath the functional film is a crystalline oxide, in particular doped with at least one other element such as aluminum, in particular It is a wet antireflection film based on zinc oxide.

  The invention further relates to a glazing unit incorporating at least one substrate according to the invention and optionally accompanied by at least one other substrate, in particular a double or triple glazing unit. Composite glazing unit or laminated glazing unit, and in particular, a laminated glazing unit with means for electrical connection to a thin film multilayer body to enable production of a heated laminated glazing unit, the substrate being Is bent and / or strengthened.

  Each substrate of the glazing unit may be transparent or colored. The at least one substrate may in particular be made of glass that is colored throughout. The choice of tint type depends on the level of light transmission required for the manufactured glazing unit and / or the colorimetric appearance.

  The glazing unit according to the invention has a laminated structure, in particular at least two rigid glass substrates bonded together with at least one thermoplastic polymer sheet so as to provide a glass / thin film multilayer / sheet / glass structure. You may do it. The polymer may in particular be based on polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), polyethylene terephthalate (PET) or polyvinyl chloride (PVC).

  In this case, the glazing unit can have a glass / thin film multilayer / polymer sheet (s) / glass structure.

  The glazing unit according to the present invention can withstand heat treatment without damaging the thin film multilayer body. Thus, they are optionally bent and / or strengthened.

  The glazing unit is composed of a single substrate having a multilayer body and can be bent and / or strengthened. The glazing unit is then called “integrated”. When the glazing unit is bent, particularly for the purpose of producing automotive glazing, the thin-film multilayer is preferably arranged at least partially on a non-planar surface.

  The glazing unit may also be a composite glazing unit, in particular a double glazing unit, wherein at least the substrate supporting the multilayer body is optionally bent and / or reinforced. In the configuration of the composite glazing unit, the multilayer body is preferably arranged so as to be adjacent to the intermediate gas-filled cavity. In the laminated structure, the base material that supports the multilayer body can be in contact with the polymer sheet.

  The glazing unit may also be a triple glazing unit consisting of three glass plates each separated by a gas-filled cavity. In a triple glazing structure, the substrate that supports the multilayer can be on surface 2 and / or surface 5 when incident sunlight is considered to pass through multiple surfaces in increasing order.

  When the glazing unit is a monolithic, composite (double or triple) or laminated glazing unit, at least the substrate that supports the multilayer body can be made of curved or tempered glass, the substrate being covered by the multilayer body. Bending or strengthening before or after deposition.

  The present invention also provides a glazing unit having a high energy reflectivity and / or a glazing unit having a very low emissivity and / or a heated glazing unit having a transparent coating heated by Joule heating. It also relates to the use of a substrate according to the invention.

  The invention also relates to the use of a substrate according to the invention for the production of transparent electrodes for electrochromic glazing units, lighting devices, display devices or photovoltaic panels.

  The substrates according to the invention are used in particular for the production of heated transparent coatings for substrates with high energy reflectivity and / or substrates with very low emissivity and / or heated glazing units. May be.

  The substrate according to the invention is in particular an electrochromic glazing unit (which is a monolithic, composite (double or triple) or laminated glazing unit), lighting device, display screen or transparent electrode of a photovoltaic panel. May be used to manufacture. (Here, the term “transparent” is understood to mean “not opaque”.)

With the multilayer according to the invention, very low sheet resistance, high light transmission (> 70%, and> 72% when laminated), low light reflectance (<14% when laminated) ) And a reflection color that is not excessively conspicuous (the a ^* coordinate and b ^* coordinate of the Lab system are close to zero, or in any case, less than +2 for a ^* ), and further, a reflection color that does not vary greatly as a function of viewing angle. It is possible to obtain.

  Specifically, at least one in the first antireflective coating below the first functional film without providing a high refractive index antireflective film in the intermediate antireflective coating, each disposed between the two functional films. By providing one high refractive index anti-reflective coating and at least one high refractive anti-reflective coating in the last anti-reflective coating on the last functional film. It would be possible to obtain a reflected color that is very close to zero and has very little variation as a function of viewing angle, while increasing the light transmission without significantly increasing the cost (this is This is because, in general, a high refractive index anti-reflection film is more difficult to deposit than a medium refractive index anti-reflection film and is expensive compared to a medium refractive index anti-reflection film)

  The multilayer antireflective coating according to the invention does not comprise an absorptive film.

  Furthermore, by utilizing a functional film thickness distribution that decreases with respect to the substrate, very low sheet resistance can be obtained for multilayers, while the reflected color as a function of angle is the thickness. Although not as good as that obtained by increasing the distribution of, it remains acceptable, while the variation in reflected color as a function of angle remains acceptable.

  However, in that case, it is important that the difference in thickness between one functional film and another in the direction of the base material or away from the base material is not so large. This is why α ≧ 0.5, preferably α ≧ 0.55, or α ≧ 0.6.

  The details and advantageous features of the present invention will become apparent from the following non-limiting examples which are described with reference to the accompanying drawings.

A multilayer body having three functional films according to the present invention, each functional film having an overblocker layer without having an underblocker layer, and further having an optional protective coating FIG. A multilayer body with four functional films according to the present invention, each functional film having an underblocker layer, not having an overblocker layer, and further having an optional protective coating. It is a figure which shows a multilayer body.

  In FIGS. 1 and 2, the thicknesses of the various layers are not shown to scale for ease of reading.

  FIG. 1 shows a multilayer structure including three functional films 40, 80, and 120, which is deposited on the transparent glass substrate 10.

  Each functional film 40, 80, 120 is disposed between the two antireflection coatings 20, 60, 100, 140, and the first functional film 40 is between the antireflection coatings 20, 60 as viewed from the substrate. The second functional film 80 is disposed between the antireflection coatings 60 and 100, and the third functional film 120 is disposed between the antireflection coatings 100 and 140.

  Each of these anti-reflection coatings 20, 60, 100, 140 comprises at least one anti-reflection coating 25/24, 28; 62, 65/64, 68; 102, 105/104, 108; 145/144. .

  Optionally, each functional film 40, 80, 120 may, on the one hand, be deposited on an underlying anti-reflection coating and an underblocker layer (not shown) located between the functional films, Alternatively, on the other hand, each functional film may be deposited directly under the overblocker layers 55, 95, 135 located between the functional film and the antireflection coating on the film.

  FIG. 1 shows a multilayer body finished with an optional protective film 200 which is not present in the following examples. In general, this overcoat is very thin and is not considered in defining the optical properties of the final antireflective coating of the multilayer body.

  In all the following examples, the thin-film multilayer body is deposited on a 1.6 mm thick transparent soda-lime glass substrate marketed by the company Saint-Gobain.

  In the following examples, the deposition conditions of the film deposited by sputtering (magnetron sputtering) are as follows.

  A first set of four examples was made. These examples are numbered 1-4 below. All four were incorporated into a laminated glazing structure of 1.6 mm thick glass substrate / 0.76 mm thick PVB laminated intermediate layer / 1.6 mm thick glass substrate supporting the multilayer body.

  Table 2 below organizes the material of each layer, the thickness in nanometer units, and the configuration of each layer forming the multilayer body in the order of the position of each layer with respect to the base material supporting the multilayer body (bottom row in the table). The numbers in the first column and the second column correspond to the reference numerals in FIG.

  Each anti-reflective coating 20, 60, 100 under the functional film 40, 80, 120 is finally provided with a wet film 28, 68, 108 based on crystalline zinc oxide doped with aluminum. These films are in contact with the functional films 40, 80, 120 deposited immediately above.

Each anti-reflective coating 20, 60, 100, 140 is
A medium refractive index anti-reflective film based on aluminum-doped silicon nitride, referred to herein as SiAl for simplicity, but the true nature of the film is actually Si ₃ N as previously described ₄ : Medium refractive index antireflection film 24, 64, 104, 144, which is Al, or
A high refractive index antireflective coating based on zirconium nitride doped silicon nitride, referred to herein as SiZrN for simplicity, but the true nature of the film is actually Si ₃ N as previously described. ₄ : High refractive index antireflection coating 25, 65, 105, 145 which is Zr,
One of them.

  These films are important for obtaining an oxygen barrier effect during heat treatment.

  In addition, these four examples have the advantage that they can be strengthened and bent.

  The total thickness of the functional film and the distribution of the thickness of the functional film are the same in these four examples, so that the multilayers have the same sheet resistance, but they have the same light transmittance. Does not have light reflectance or color.

  Table 3 shows the sheet resistance after heat treatment (bending at 640 ° C.) measured for each substrate supporting the multilayer body and the completed laminated glazing unit incorporating the substrate supporting the multilayer body for Examples 1 to 4. This is a summary of the main optical characteristics measured for the.

For these substrates,
_TL indicates the light transmittance in the visible range in% measured with a 10 ° observer under the A light source,
_RL indicates the light reflectance in the visible range in% measured with a 10 ° observer under A light source,
・ R _□ indicates the multilayer sheet resistance in units of Ω / □ after heat treatment (bending)
A _R0 ^* and b _R0 ^* are measured under a D65 light source using a 10 ° observer, and thus reflect the Lab coordinates a ^* and b ^* of the reflected color, measured substantially perpendicular to the glazing unit. Show
A _R60 ^* and b _R60 ^* are the Lab coordinates a ^* and b ^* of the reflected color measured at an angle of 60 ° perpendicular to the glazing unit under a D65 light source using a 10 ° observer. Show.

  Thus, comparing Example 2 with Example 1, the antireflection barrier films 25, 65, 105, and 145 made of SiZrN are used in place of the antireflection barrier films 24, 64, 104, and 144 made of SiAlN. The light transmittance of the glazing unit can be increased by more than 1%, while the light reflectance remains substantially the same, and the reflection color at 0 ° and 60 ° can be allowed to be acceptable. Is observed.

  However, Example 2 is difficult to implement on an industrial production line. The reason is that the central antireflection barrier films 65 and 105 made of SiZrN, that is, two functional films arranged on both sides are thick (58 nm).

  When Example 3 is compared with Examples 1 and 2, only the central antireflection barrier films 65 and 105 made of SiZrN are used in place of the central antireflection barrier films 64 and 104 made of SiAlN. In addition, when the last antireflection barrier films 24 and 144 are made of SiAlN, it can be seen that the light transmittance of the glazing unit cannot be significantly increased (by an increase of only about + 0.2%).

The SiAlN film and the SiZrN film have an extinction coefficient k of less than 0.01, the extinction coefficient k of SiAlN at 550 nm is about 1.3 × 10 ⁻⁵ , and the extinction coefficient k of SiZrN at 550 nm is about 7 .5 is a × 10 ^-5.

  Comparing Example 4 with Examples 1-3, the first and last high refractive index antireflection barriers made of SiZrN instead of the first and last medium refractive index antireflection barrier films 24, 144 made of SiAlN. By using only the films 25 and 145 and making each of the middle refractive index antireflection barrier films 64 and 104 with SiAlN, the light transmittance of the glazing unit can be remarkably increased as in Example 2. It can be seen (about + 1%), but this example is simpler and easier to implement than Example 2 and is less expensive.

  In this set of Examples 1-4, only Example 4 is an example according to the present invention because of the anti-reflective coating 20 disposed below the first functional film 40 as viewed from the substrate and the substrate. The antireflection coating 140 disposed on the last functional film 120 to be viewed includes at least one high refractive index antireflection film 25, 145, respectively, and each reflection disposed between the two functional films. This is because the anti-reflection coatings 60 and 100 do not include a high refractive index anti-reflection film.

  Example 1 is not an example according to the present invention because none of the antireflective coatings 20, 60, 100, 140 includes a high refractive index antireflective coating.

  Example 2 is not an example according to the present invention because antireflective coatings 20, 60, 100, 140 all contain a high index antireflective coating.

  Example 3 also has both an anti-reflective coating 20 disposed below the first functional film 40 as viewed from the substrate and an anti-reflective coating 140 disposed on the last functional film 120 as viewed from the substrate. The anti-reflective coatings 60 and 100 disposed between the two functional films do not include at least one high-refractive index anti-reflective film, and include the high-refractive index anti-reflective films 65 and 105. Again, this is not an example according to the present invention.

  In this set of Examples 1-4, the thickness of the three silver films in each example was the same, all 13 nm.

  A second set of four examples was made using the same deposition conditions (Table 1) as the first set. These examples are numbered 5-8 below. All four were incorporated into a laminated glazing structure of 1.6 mm thick glass substrate / 0.76 mm thick PVB laminated intermediate layer / 1.6 mm thick glass substrate supporting the multilayer body.

  In the second set, the total thickness of the functional film in each example was the same, and the total thickness of the functional film in the example of the first set was the same. However, unlike the first set of examples, the three functional films are not all the same thickness, and the functional film (Ag1) closest to the substrate is thicker than the next film (Ag2), and this film (Ag2) The film itself was thicker than the next film (Ag3). Therefore, in the sets of Examples 5 to 8, the thickness distribution of the functional film is reduced as viewed from the base material. As a result, the application number PCT / FR2010 / 051732 was filed in International Publication No. 2011/020974 pamphlet. Follow the teachings of published international patent applications.

  Table 4 below shows, for Examples 5-8, the material of each layer and the thickness in nanometers, and the configuration of each layer forming the multilayer body, and their relationship to the substrate supporting the multilayer body (bottom row of the table). Arranged in order of position, the numbers in the first column and the second column correspond to the reference numerals in FIG.

The thickness e _x of each functional film 80, 120 is smaller than the thickness of the preceding functional film in the direction of the substrate 10, and is such that the expression e _x = αe _x−1 ,
X is the column number of the functional film as seen from the substrate 10
X-1 is the column number of the functional film located in the front in the direction of the substrate 10,
Α is a number such that 0.5 ≦ α <1, preferably 0.55 ≦ α ≦ 0.95, or 0.6 ≦ α ≦ 0.95;
The thickness of the first metal functional film 40 as viewed from the substrate is such that 10 nm ≦ e ₁ ≦ 18 nm, preferably 11 nm ≦ e ₁ ≦ 15 nm.

The thickness e ₂ of the second function film 80 is e ₂ = 0.87e _1, hence an alpha = 0.87, the thickness e ₃ of the third functional film 120 is e ₃ = 0.85E ₂ and therefore α = 0.85. The value of α is different for all functional films in the second row of the multilayer body or later (only 0.02).

  Table 5 shows the sheet resistance after heat treatment (bending at 640 ° C.) measured for each base material supporting the multilayer body and the finished laminated glazing unit incorporating the base material supporting the multilayer body for Examples 5 to 8. The main optical properties measured for are summarized and all these measurements were made in the same manner as in Examples 1-4.

  Thus, comparing Example 6 with Example 5 in this second set of examples, antireflection barrier films 25, 65, 105 made of SiZrN instead of making each of the antireflection barrier films 24, 64, 104, 144 made of SiAlN. 145 can increase the light transmission of the glazing unit by more than 1%, while the light reflectance remains substantially the same, allowing reflection colors at 0 ° and 60 °. It is acknowledged that it can be kept in the stuff.

  However, Example 6 is difficult to implement on an industrial production line. The reason is that the central antireflection barrier films 65 and 105 made of SiZrN, that is, two functional films arranged on both sides are thick (58 nm).

  Comparing Example 7 with Example 5 and Example 6, only the central antireflection barrier films 65 and 105 made of SiZrN were used instead of making each of the central antireflection barrier films 64 and 104 of SiAlN, and the first and It can be seen that when the last antireflection barrier films 24 and 144 are made of SiAlN, the light transmittance of the glazing unit cannot be significantly increased (by an increase of only about + 0.2%).

  Comparing Example 8 with Examples 5-7, instead of the first and last antireflection barrier films 24, 144 made of SiAlN, only the first and last antireflection barrier films 25, 145 made of SiZrN were used. It can be seen that by using each of the central antireflection barrier films 64 and 104 made of SiAlN, the light transmittance of the glazing unit can be remarkably increased (about + 1%) as in Example 6. However, this example is simpler and easier to implement than Example 6 and is less expensive.

  In this set of Examples 5-8, only Example 8 is an example according to the present invention because the anti-reflective coating 20 disposed below the first functional film 40 as viewed from the substrate and the substrate Each antireflection coating 140 disposed on the last functional film 120 to be viewed includes at least one high refractive index antireflection film 25, 145, and each antireflection coating disposed between the two functional films. This is because the coatings 60 and 100 do not include a high refractive index antireflection film.

  Example 5 is not an example according to the present invention because none of the antireflective coatings 20, 60, 100, 140 includes a high refractive index antireflective coating.

  Example 6 is not an example according to the present invention because anti-reflective coatings 20, 60, 100, 140 all contain a high index anti-reflective coating.

  Example 7 also has both an anti-reflective coating 20 disposed below the first functional film 40 as viewed from the substrate and an anti-reflective coating 140 disposed on the last functional film 120 as viewed from the substrate. The anti-reflective coatings 60 and 100 disposed between the two functional films do not include at least one high-refractive index anti-reflective film, and include the high-refractive index anti-reflective films 65 and 105. Again, this is not an example according to the present invention.

  Furthermore, since the total thickness of the silver film is large (thus low sheet resistance is obtained) and the optical properties (especially the light transmittance in the visible region) are good, the substrate coated with the multilayer body according to the present invention is used. Thus, it is possible to produce a transparent electrode substrate.

In this transparent electrode substrate, in particular, part of the zirconium nitride silicon antireflection film 145 of Example 4 is replaced with a conductive film (especially having a resistivity of less than 1 × 10 ⁵ Ω · cm), and in particular, an oxide is used as a base material. It can be suitable for organic light emitting devices when substituting. This film is for example formed of tin oxide, optionally based on Al or Ga, based on zinc oxide, or mixed oxides, in particular tin oxide (ITO), indium zinc oxide (IZO). ), Or optionally (eg, Sb and / or F) doped zinc tin oxide (SnZnO). You may use this organic light-emitting device for manufacture of an illuminating device or a display apparatus (screen).

  FIG. 2 shows a multilayer structure including four functional films 40, 80, 120, and 160 that is deposited on the transparent glass substrate 10.

  Each functional film 40, 80, 120, 160 is disposed between the two antireflection coatings 20, 60, 100, 140, 180, and the first functional film 40 as viewed from the substrate is the antireflection coating 20, 60, the second functional film 80 is disposed between the antireflection coatings 60, 100, the third functional film 120 is disposed between the antireflection coatings 100, 140, and the fourth function. A film 160 is arranged between the antireflection coatings 140, 180.

  These antireflective coatings 20, 60, 100, 140, 180 are each at least one antireflective coating 25/24, 28; 62, 65/64, 68; 102, 105/104, 108; 145/144, 148. 184/185.

  Optionally, each functional film 40, 80, 120, 160, on the other hand, is deposited on an underblocker layer 35, 75, 115, 155 disposed between the lower antireflection coating and the functional film. Alternatively, each functional film may be deposited directly on an overblocker layer (not shown) disposed between the functional film and the upper antireflection coating.

  FIG. 2 shows a multilayer finished with an optional protective film 200, in particular a film based on oxide, in particular a film that is stoichiometrically deficient in oxygen.

  Each anti-reflective coating 20, 60, 100, 140 under the functional film 40, 80, 120, 160 is finally a wet anti-reflective film 28, 68 based on crystalline zinc oxide doped with aluminum. , 108, and 148, and these films are in contact with the functional films 40, 80, 120, and 160, respectively, deposited immediately above.

Each anti-reflective coating 20, 60, 100, 140, 180 is
A medium refractive index antireflective film based on aluminum-doped silicon nitride, referred to herein as SiAlN for simplicity, but the true nature of the film is actually Si ₃ N as previously described. ₄ : Medium refractive index antireflection film 24, 64, 104, 144, 184, which is Al, or
A high refractive index antireflective coating based on zirconium nitride doped silicon nitride, referred to herein as SiZrN for simplicity, but the true nature of the film is actually Si ₃ N as previously described. ₄ : High refractive index antireflective coating 25, 65, 105, 145, 185, which is Zr,
One of them.

  These films are important for obtaining an oxygen barrier effect during heat treatment.

  A third set of four examples was made using the same deposition conditions (Table 1) as the first and second sets. These examples are numbered 9-12 below. All four were incorporated into a laminated glass structure of 1.6 mm thick glass substrate / multilayer body supporting 0.76 mm thick PVB laminated interlayer / 1.6 mm thick glass substrate.

  In this third set, the total thickness of the functional films in each example was the same, and all the four functional films were the same thickness.

  Table 6 below shows, for Examples 9-12, the material of each layer and the thickness in nanometers, and the configuration of each layer forming the multilayer body, and their relationship to the substrate supporting the multilayer body (bottom row of the table). In the table arranged in order of position, the numbers in the first column and the second column correspond to the reference numerals in FIG.

  Table 7 shows the sheet resistance after heat treatment (bending at 640 ° C.) measured for each substrate supporting the multilayer body for Examples 9 to 12, and the finished laminated glazing unit incorporating the substrate supporting the multilayer body. The main optical properties measured for are summarized and all these measurements were made in the same manner as in Examples 1-8.

  Thus, comparing Example 10 with Example 9 in this third set of examples, antireflection barrier films 25, 65 made of SiZrN instead of making each of the antireflection barrier films 24, 64, 104, 144, 184 from SiAlN. , 105, 145, and 185, the light transmittance of the glazing unit can be increased by almost 1%, while the reflectance of the light remains substantially the same, and the reflected colors at 0 ° and 60 ° are obtained. It will be appreciated that it can only be acceptable.

  However, Example 10 is difficult to implement on an industrial production line. The reason is that the central antireflection barrier films 65, 105, and 145 made of SiZrN, that is, two functional films arranged on both sides are thick (58 nm).

  When Example 11 is compared with Example 9 and Example 10, only the central antireflection barrier films 65, 105, and 145 made of SiZrN are used in place of the central antireflection barrier films 64, 104, and 144 made of SiAlN. It can be seen that when the first and last antireflection barrier films 24, 184 are made of SiAlN, the light transmittance of the glazing unit cannot be significantly increased (by an increase of only about + 0.2%).

  Comparing Example 12 with Examples 9-11, instead of the first and last antireflection barrier films 24, 184 made of SiAlN, only the first and last antireflection barrier films 25, 185 made of SiZrN are used. In addition, it can be seen that the light transmittance of the glazing unit can be remarkably increased as in Example 10 by making each of the central antireflection barrier films 64, 104, and 144 with SiAlN. Simpler than 10 and easier to implement and less expensive.

  In this set of Examples 9-12, only Example 12 is an example according to the present invention because of the anti-reflective coating 20 disposed below the first functional film 40 as viewed from the substrate and the substrate. Each antireflection coating 180 disposed on the last functional film 160 to be viewed includes at least one high refractive index antireflection film 25, 185, and each antireflection film disposed between the two functional films. This is because the coatings 60, 100, and 140 do not include a high refractive index antireflection film.

  Example 9 is not an example according to the present invention because none of the antireflective coatings 20, 60, 100, 140, 180 includes a high refractive index antireflective coating. Example 10 is not an example according to the present invention because anti-reflective coatings 20, 60, 100, 140, 180 all contain a high refractive index anti-reflective coating. Example 11 also includes an antireflection coating 20 disposed below the first functional film 40 as viewed from the substrate and an antireflection coating 180 disposed on the last functional film 160 as viewed from the substrate. The antireflective coatings 60, 100, 140, which do not include at least one high refractive index antireflection film and are disposed between the two functional films, are provided with the high refractive index antireflection films 65, 105, 145. This is not an example according to the present invention.

  In general, the transparent electrode substrate may be suitable for use as a heating substrate in a heated glazing unit, particularly in a heated laminated windshield. It may also be suitable for use as a transparent electrode substrate for any electrochromic glazing unit, any display screen, or for use in a photovoltaic cell, particularly as the front or back surface of a transparent photovoltaic cell.

  The present invention has been described above as an example. Of course, those skilled in the art can derive various modifications of the present invention without departing from the scope of the patent as defined by the claims.

Claims (11)

  A substrate (10), in particular a transparent glass substrate, "n" functional metal films (40, 80, 120), in particular metal functional films based on silver or silver-containing metal alloys; (N + 1) "anti-reflective coatings (20, 60, 100, 140), each functional film (40, 80, 120) placed between two anti-reflective coatings (20, 60, 100, 140) A substrate provided with a thin film multilayer body, wherein n is an integer of 3 or more, and each antireflection coating includes at least one antireflection film, as viewed from the substrate The antireflection coating (20) disposed under the first functional film (40) and the antireflection coating disposed over the last functional film as viewed from the substrate are each at least 1 High refractive index antireflection (25, 145) and each of the multilayer bodies is 2.15 so that each antireflective coating (60, 100) disposed between the two functional films does not include a high refractive index film. A base material (10) comprising at least two high refractive index antireflection films (25, 145) having the above refractive indexes.   The antireflective coating (20) disposed under the first functional film (40) when viewed from the base is, in order from the base, one or more high-refractive index antireflective films (25) and , Followed by a crystalline oxidation having a refractive index between 1.60 and 2.15, excluding these values, optionally doped with at least one other element such as aluminum Base material (10) according to claim 1, characterized in that it comprises a medium refractive index wet antireflective film (28) based on a material, in particular zinc oxide.   The base material according to claim 1 or 2, wherein the antireflection coating disposed on the last functional film as viewed from the base material is composed of only one or more high refractive index antireflection films. (10).   4. The substrate (10) according to any one of claims 1 to 3, characterized in that at least one or each high refractive index antireflection film (25, 145) is based on zirconium nitride silicon. The thickness e _{x of} each functional film (80, 120) is smaller than the thickness of the preceding functional film in the direction of the substrate (10), and e _x = αex ₋₁
(Where
X is the row number of the functional membrane as seen from the substrate (10),
X-1 is the row number of the functional film preceding in the direction of the substrate (10),
Α is a number such that 0.5 ≦ α <1, preferably 0.55 ≦ α ≦ 0.95, or 0.6 ≦ α ≦ 0.95)
And
The thickness of the first metal functional film as viewed from the substrate is 10 nm ≦ e ₁ ≦ 18 nm, preferably 11 nm ≦ e ₁ ≦ 15 nm,
The substrate (10) according to any one of claims 1 to 4, characterized in that it has a thickness.   The substrate (10) according to claim 5, characterized in that the value of α is different for all functional films in the second row and thereafter.   The total thickness of the functional metal film is preferably greater than 30 nm, in particular between 30 nm and 60 nm, including these values, or the total thickness is a thin-film multilayer comprising three functional films 7 or between 35 nm and 50 nm, or the total thickness is between 40 nm and 60 nm in a thin film multilayer body with four functional films. (10).   Each of the antireflective coatings (60, 100) disposed between two functional films that do not include a high refractive index antireflective film is optionally nitrided with at least one other element such as aluminum. 8. Substrate (10) according to any one of the preceding claims, characterized in that it comprises at least one antireflection film (64, 104) based on silicon.   A crystalline oxide, in particular zinc oxide, in which the last film of each antireflection coating under the functional film (40, 80, 120) is optionally doped with at least one other element such as aluminum A substrate (10) according to any one of the preceding claims, characterized in that it is a wet antireflective film (28, 68, 108) based on.   A glazing unit, in particular a double or triple, in which at least one substrate (10) according to any one of claims 1 to 9 is incorporated and optionally accompanied by at least one other substrate. A laminated glazing unit comprising means for electrically connecting to said thin film multilayer body to enable production of a composite glazing unit or laminated glazing unit, such as a glazing unit, and in particular a heated laminated glazing unit, comprising: A glazing unit in which the substrate supporting the multilayer body is optionally bent and / or reinforced.   10. A heated transparent coating for a heated glazing unit, or a transparent electrode for an electrochromic glazing unit, lighting device, display device or photovoltaic panel. Use of the substrate described in 1.

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